Detergent composition



United States Patent 3,332,880 DETERGENT COMPOSITION Adriaan Kessler, Cincinnati, and Phillip F. Pflaumer, Colerain Township, Hamilton County, Ohio, assignors to The Procter & Gamble Company, Cincinnati, Ohio, a corporation of Ohio No Drawing. Filed June 29, 1966, Ser. No. 561,397 12 Claims. (Cl. 252-161) This is a continuation-in-part patent application of copending application Ser. No. 516,139, filed Dec. 23, 1965, now abandoned, which is a continuation of patent application Ser. No. 423,364, filed Jan. 4, 1965, now abandoned.

This invention relates to novel detergent compositions, and especially, to detergent compositions which offer excellent overall performance characteristics. It also relates to built detergent compositions useful in light-duty and heavy-duty cleaning situations.

The need for improved detergent compositions is a continuing one. The search for such compositions receives a great deal of attention by the chemical and allied industries. Countless new surface active materials have been and are being prepared of which only a relatively few may eventually be found suitable for commercial use as detergent materials in applications such as toilet bars, dishwashing compositions, as well as light-duty and heavyduty built laundering compositions. Relatively so little is known about the complex nature of detergency and the role which a detergent plays in a cleaning process that the element of predictability as to which surface active compounds will work well and which will not, is almost negligible.

Special attention is given to the preparation of detergent compounds which are useful in dishwashing and laundering compositions. These applications are generally referred to by such terms as light-duty and heavyduty. These terms as applied to detergency have acquired fairly definite meanings in the art.

Light-duty applications are those such as the hand washing of dishes and lightly soiled fine fabrics which fabrics cannot as a rule withstand the vigorous treatment of machine laundering. Also, light-duty washing situations are those which generally call for a gentle washing action in cool or lukewarm water. It is well known by those skilled in the art that compositions designed for such uses must have certain performance properties which distinguish them from heavy-duty cleaning compositions; For instance, they must be mild to the skin, possess high sudsing properties, and also possess cleaning power in water solutions having cool or luke warm temperatures, e.g., below 100 F.

The term heavy-duty applications are those cleaning situations in which heavily soiled articles are encountered. Considerations in such cleaning processes in-; clude the use of vigorous mechanical action usually in hot water having temperatures between about 120 F.

up to about 200 F. Moreover, the problems presented by high soil loads or fabrics such as cotton are unlike those dealt with .in light-duty situations. As a result, heavy-duty detergent compositions must be specially formulated.

In the formulation of heavy-duty built detergent laundering compositions, the most valuable detergents are those which combine effective cleaning ability with superior whiteness maintenance results. Cleaning pertains to the removal of soil from soiled articles. Whiteness maintenance is a term which is used to measure the ability of an aqueous solution of a detergent composition to keep suspended in the solution, soil which has been removed during the washing process.

There has long been a need for a built detergent com- 3,332,880 Patented July 25, 1967 "ice position which can be used with superior effectiveness in both light-duty and heavy-duty cleaning situations. This implies, of course, satisfactory performance in washing solutions where temperature ranges anywhere from about 50 F. up to about 200 F. and higher. Literally thousands of active detergent compounds have been tried, alone and in combination with other detergents and builders, as well as other detergent aids such as sequestering agents in order to satisfy this need of longstanding. For the most part, such attempts have not been satisfactory.

Accordingly, it is an object of the present invention to provide an improved detergent composition which has excellent overall detergent properties. It is another object of the present invention to provide an active detergent composition which is outstandingly suitable for lightduty and heavy-duty cleaning applications as described above.

Another object is to provide a built detergent composition containing an active detergent ingredient and a builder ingredient which provides excellent performance results when used in a washing solution having a temperature which can be between about 50 F. up to about 200 F. Still another object is to provide a less expensive, more efficient built detergent composition than the best commercially available compositions. A further object is to provide a built detergent composition which is especially effective even in the presence of increasing soil loads. Yet another object is to provide a built detergent composition which in aqueous solutions at about F. cleans as well as, or better than, the best conventional detergent compounds clean at higher temperatures on the order of about F. Yet another object is to provide a built detergent composition which not only excels at cleaning, i.e., the removal of soil, but also offers superior whiteness maintenance results in cool water as well as in hot water. These and other objects of the present invention will become apparent from the following detailed description. All percentages used hereinafter in the specification and claims are by weight unless otherwise specified.

According to the present invention, a detergent composition possessing the foregoing exceptional performance properties is provided, which comprises by weight from about 30% to about 70% of Component A, from about 20% to about 70% of Component B, and from about 2% to about 15% of Component C, wherein:

(a) Said Component A is a mixture of double-bond positional isomers of water soluble salts of alkene-l-sulfonic acids containing from about 10 to about 24 carbon atoms, said mixture of positional isomers including by weight about 10% to about 25% of an alpha-beta unsaturated isomer, about 30% to about 70% of a betagamma unsaturated isomer, about 5% to about 25 of a gamma-delta unsaturated isomer, and about 5% to about 10% of a delta-epsilon unsaturated isomer;

(b) Said Component B is a mixture of water soluble salts of bifunctionally-substituted sulfur-containing saturated aliphatic compounds containingfrom about 10 to about 24 carbon atoms, the functional units being hydroxy and sulfonate radicals with the sul'fonate radical always being on the terminal carbon and the hydroxyl radical being attached to a carbon atom at least two carbon atoms removed from the terminal carbon atom; and

(c) Said Component C is a mixture comprising from 30-95% water-soluble salts of alkene disulfonates containing from about 10 to about 24 carbon atoms, and from about 5% to about 70% water-soluble salts of hydroxy disulfonates containing from about 10 .to about 24 carbon atoms.

Said alkene disulfonates containing a sulfonate group attached to a terminal carbon atom and a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, the alkene double bond being distributed between the terminal carbon atom and about the seventh carbon atom, said hydroxy disulfonates being saturated aliphatic compounds having a sulfonate radical attached to a terminal carbon, a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, and a hydroxy group attached to a carbon atom which is not more than about four carbon atoms removed from the site of attachment of said second sulfonate group.

It is desirable to include each of the three basic Components described above as Components A, B, and C in the prescribed percentage ranges in order for the composition to possess the overall outstanding detergent properties discovered and provided by the present invention. Preferred percentage ranges by Weight for the Components are from about 35% to about 65% of Component A, from about 25% to about 60% of Component B, and from about 3% to about 12% of Component C.

Each of the Components will now be described more fully as to their composition.

Component A is comprised essentially of the following compounds in the prescribed ranges:

In the preceding formulas, x is an integer of from about 4 to about 18, preferably from about 4 to about 12., and M represents any cation that forms a water-soluble salt such as alkali metals, e.g., sodium and potassium, and ammonium, and substituted ammonium compounds, e.g., trialkylammonium and trialkylolammonium compounds. Specific examples of substituted ammonium compounds are triethylammonium, trimethylammonium, and triethanolammonium. Others will be apparent to those skilled in the art. The symbols x and M have the same meaning throughout the description of the present invention. There can also be present minor amounts of other double-bond positional isomers. This is the case, for example, when the composition is .prepared by the sulfonation of alpha olefins with uncomplexed sulfur trioxide. Such minor amounts, i.e., less than by weight, do not materially alter the excellent detergent properties of the composition.

Whereas, Component A is a blend or mixture of certain unsaturated isometric aliphatic compounds, Component B consists of a mixture of saturated aliphatic compounds. A minor amount of unsaturation can be included in this mixture but preponderantly the com-pounds are all saturated. The bifunctionality of these alkane compounds is due to the presence of a hydroxyl group and a sulfonate radical on the same molecule. It has been discovered that the sulfonate radical must be located on the terminal carbon. It also has been discovered that the situs of the hydroxyl group in the compounds that comprise Component B is an especially important factor. For example, if the bifunctional groups, i.e., the hydroxyl group and the sulfonate radical, are attached to adjacent carbon atoms, the valuable detergent properties of the Component B compounds are substantially decreased. This is especially true when the alpha and beta carbons are the two sites of attachment. The critical structural arrangement which must exist in order for the compounds to be detergents is that the sulfonate radical must be in the alpha position and the hydroxyl group must be attached to a carbon at least two carbons removed,

. and zeta-eta unsaturation. Preferably,

]?ermis- Presible ferred Range, Range, Percent Percent CHa(CH2)xCHzOHzCH(OH) CHrOHzSOsM. 10-90 25-75 C H3(CH2) XCHZGH OH) CHzCHzCHzS 03M. 10-90 25-75 OH3(CH2)X CH(OH) OHZCH CHBOHZS 0 M. 10-90 25-75 The value for x and M are as previously set forth.

The 3-, 4-, and S-hydroxy sulfonates, and mixtures thereof, have been discovered to be such superior detergent compounds when used as the sole active ingredient in built compositions that such compositions, per se, represents a preferred embodiment of the present invention. This aspect of the present invention is described more fully hereinafter.

Component B can also include minor quantities, for example, less than 10%, of compounds wherein the hydroxyl group is attached elsewhere along the carbon chain, e.g., on the sixth carbon atom, without materially altering the overall detergent properties of the compositions. However, at least of the hydroxy radical substitutions must be in the 3, 4 and 5 positions. The 3-, 4-, 5- hydroxy sulfonate compounds, illustrated above, are preferred both as ingredients comprising Component B and also as sole detergent actives in built detergent systems.

In this same connection, it has also been noted that the beta-hydroxy sulfonate compound performs unsatisfactorily as a detergent compound. Not only is it not a good detergent, but it has been discovered surprisingly that such a compound constitutes an actual load on the present detergency system. For this reason, the level of such a compound should be held to a minimum. By some sulfonation processes, beta-hydroxy sulfonates are formed in minor amounts. Such minor amounts can be tolerated in the composition of this invention provided that Components A, B, and C otherwise contain the other ingredients herein described in the proportions and percentages specified.

The alkene disulfonates should from about 40% to about 80% of the highly polar polyfunctionally substituted aliphatic compounds which make up Component C. These alkene disulfonates should preferably contain from about 10 to about 18 carbon atoms. As mentioned above, one sulfonate group is attached to the terminal carbon atom. The second sulfonate group is attached to an internal carbon atom that is not more than about six carbon atoms removed from the terminal carbon. In other words, the second sulfonate functional group can be attached to the second through about the seventh carbon atom. Component C can also include minor amounts of compounds in which the second sulfonate is located more internally than the seventh carbon, such as, for example, on the eighth carbon, etc. There is no apparent advantage in having these latter compounds present in the composition, however. According to a preferred embodiment, the major portion that is from about 60% to about of the alkene disulfonates should be 1.2 to 1.3 disulfonates.

The alkene double bond can be distributed between the terminal carbon and about the seventh carbon atom; such unsaturation includes, for instance, alpha-beta, beta-gamma, gamma-delta, delta-epsilon, epsilon-zeta, the double bond should be distributed between the second to the sixth carbon atom. It should be noted that the alkene double preferably comprise bond can be even more internally located than between the zeta-eta carbons, but again no apparent advantage is gained thereby.

Thus, it can be seen that the alkene disulfonates of component C contain the polyfunctional combination of a double bond and two sulfonate groups in an important structural relationship. The preferred compounds as ingredients of the alkene disulfonate portion of Component C are 2-alkene-1,2-disulfonate; 3-alkene-l,2-disulfonate; and 4-alkene-1,2-disulfonate of the 1,2 disulfonate species; and 3-alkene-1,3-disulfonate; 4-alkene-l,3-disulfonate; and 5-alkene-1,3-disulfonate of the 1,3 disulfonate species. The alkene group can contain from about to about 24 carbon atoms and preferably about 12 to 18 carbon atoms. The sodium and potassium salts of these compounds are preferred.

Examples of alkene disulfonate compounds are the following in which a carbon chain length of 16 was selected as being representative, havingsulfonate attachment sites of 1,2 and 1,3:

As mentioned above, Component C contains -he aforementioned and illustrated alkene disulfonates. It also contains from about 5% to about 70%, and preferably about 20% to about 60%, water-solublesalts of hydroxy disulfonates containing from about 10 to about 24 carbon atoms. The terminal carbon atom has attached to it one of the sulfonate groups. The second sulfonate group can be attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom. The required hydroxy group is attached to a carbon atom which is not more than about four carbon atoms removed from the site ofattachment of said second sulfonate group.

The preferred sites of attachment for the hydroxy group on the 1,2 disulfonate species are the fourth and fifth carbon atoms to yield.4-hydroxyalkane-1,2-disulfonates and S-hydroxyalkane-l,2-disulfonates. For the 1,3-disu1fonates the preferred sites of attachment for the hydroxy group are the fifth and the sixth carbon atoms to yield S-hydroxyalkane-1,3-disulfonates and 6-hydr0xyalkane-l,3-disulfonates. The alkane hydrocarbons as before are those having 10 to 24 carbon atoms. According to a preferred embodiment, the major portion, that is, from about 60% to about95% of the hydroxy disulfonates should be 1,2 and 1,3 disulfonates. I

Thus, for example, the following compounds are contemplated. Again, a 16 carbon 1,2 and 1,3 disulfonate compound is presented as being representative.

It is postulated that a second polar group, as in Components B and C, spaced a critical distance from a terminally attached polar group in a detergent molecule modifies the crystalline latice structure in such a way as to improve markedly the solubility characteristics of the compound. While this is not known for certain, it is offered as one possible explanation for the exceptional detergent properties of the compositions of the present invention.

The novel compositions of the present invention can be prepared in any suitable manner so long as the above teachings are adhered to. For instance, each of the ingredients can be synthesized separately and then mixed according to the stated proportions. On the other hand, it is possible to prepare the compositions of the present invention according to a novel process described in copending patent application Ser. No. 423,292 filed J an. 4, 1965, by Adriaan Kessler and Phillip F. Pflaumer.

If it is desired to synthesize separately the individual components of the novel mixture, it is possible to do so according to the procedures in the following discussion. Any other suitable methods can be used. The symbol R as used in the following equation represents an aliphatic hydrocarbon radical that would allow for a total of carbon atoms in the molecule between about 10 and about 24. The alpha-beta unsaturated sulfonate containing aliphatic compounds of Component A can be prepared readily by dehydrochlorinating a 2-chlorosulfonic acid derivative. A fairly detailed discussion of a suitable preparative route appears in an article in the Journal of Organic Chemistry, vol. 1949, page 46, written by I. D. Rose and A. Lambert. The starting step for this synthesis is a reaction between a long chain epoxide and sodium bisulfite to produce a 2-hydroxy-1-sulfonate derivative of the particular long chain epoxide used. This reaction product is condensed with P01 to prepare the aforementioned 2-chlorosulfonic acid derivative which in turn is reacted with sodium carbonate to yield an alpha-beta unsaturated compound.

The other preferred double-bond positional isomers of Component A, i.e., the beta-gamma, gamma-delta, and delta-epsilon can be prepared by the thermal dehydration of hydoxy-sulfonates. According to the following reaction,

the thermal dehydration of the sodium salt of 3-hydroxysulfonate results in the preparation of a reaction mixture containing the beta-gamma isomer and the gamma-delta isomer.

nomomomomomsoma RCHzOH -CHCHZSOaNa ROH=OHOHzSOaNa The foregoing synthesis of the double-bond positional isomers follows closely the well known dehydration of an organic alcohol as is mentioned in such standard texts as Whitmores Organic Chemistry, second edition, pages 39-41.

There is no need to separate the reaction product of the two illustrated dehydration reaction. The reaction product can be formulated directly into a detergent composition according to the present invention. If, for some reason, it is desired to work with pure ingredients, they can be separated into pure forms.

The hydroxy sulfonates of Component B, such as the preferred 3-, 4-, and S-hydroxy compounds can be prepared by the free radi-cal addition of sodium bisulfite to the corresponding 3-, 4-, or S-hydroxy-l-olefin, respectively:

Free Radical Catalyst RCH(OH)CH=CH NaHSO aldehyde Grignard 4-hydr0xy-1-olefin Reagent A discussion of the conversion of hydroxyolefins produced by preceding Equations a and b to hydroxy sulfonates appears in an article writ-ten by J. Willens, Bulletin of the Chemical Society of Belgium, vol. 64, page 427 (1955).

It is to be understood that other hydroxy sulfonates as desired can be prepared by using different Grignard reagents in the reaction equation set forth above.

The alkene disulfonates and the hydroxy disulfonates which comprise Component C may also be prepared separately by any known manner. For instance, the hydroxy disulfonates may be prepared by epoxidizing olefin sultonic acid isomers, and then opening the epoxide ring with sodium bisulfite by standard reaction techniques. The hydroxy disulfonates may then be dehydrated by reactions known to those skilled in the art to yield the corresponding isomeric alkene disulfonates.

The novel compositions of the present invention are useful per se as excellent detergents. As mentioned earlier, the various compounds that make up the three components can contain from about to about 24 carbon atoms. It is preferred, however, to have the compounds contain from 12 to 18 carbon atoms. Within this narrower preferred range a carbon chain length of 16 to 18 represents a preferred embodiment. It is not necessary that each of the compounds contain the same number of carbon atoms. Mixtures of difierent chain lengths can be used. It is only critical that the number of carbon atoms in each molecule be within the above prescribed range of 10 to 24 or preferably, 12 to 18.

' The following examples illustrate the detergent compositions of the present invention wherein the percentages are by weight and wherein Components A, B and C total up to The percentages listed for each ingredient are by weight of that particular ingredient in the total composition.

EXAMPLE I Component A Percent C H CH"-=CHSO Na 13 C I-I CH CHCH SO Na 33 C H CH=CH CH CH SO Na 13 C1 1H23CH CHCH2CH2S03 Na- 6 Total 65 Component B C H CH(OH)CH CH SO N3. 20 C H CH(OH) (jHgCI'IgCIIgSO I IEI 5 Total 25 Component C C H CH=C(SO Na)CH SO Na 1.0 C12H25CH CHCH(SO3Na)CH2SO3N3- C H CH=CHCH CH(SO Na)CH SO Na CH CH SO Na C1 3N3) CH S'O Na CmH21CH CH-'CH2-CH CH CH SO Na .5 C H CH (OH CH CH (SogNa) CH SO Na 1 C1 1H25CH( (SO Na) CH2SO3N3. C H -CH-( OH ---CH -CH (SO Na) CH2CH2 SO3Na C H CH(OH CH CH -CH (SO Na) CH2'cH2S03Na 5 Total 10 This composition has detergent properties which are outstanding especially in areas of built detergent compositions.

EXAMPLE II Component A Percent C H CH=CHSO Na 9 C H CH=CHCH SO Na 34 c, -H cH=cI-IcH cH,so,eNae 12 C H CH=CHCH CH CH SO Na 10 Total Component B C H CH OH CH CH CH SO Na 10 9 Component CContinued Percent CH= CHSO Na .5 CmHg =CHCH SO Na .5 C H -CH CH CH (OH) CH CH (S Na)--CH SO Na 3.0 C H CH CH (OH )CH CH -CH (SO Na)CH SO Na 1.0 C1QH21CH2CH -CH CH SO NE1 1.0

Total 12 This composition also oifers excellent detergent properties of cleaning and whiteness maintenance when used in built detergent compositions.

It was noted above in the discussion concerning Component B that a preferred embodiment of the present invention is a built detergent composition wherein the active detergent is selected from the group consisting of water soluble 3 hydroxy n alkyl-l-sulfonates, 4- hydroxy n alkyl 1 sulfonates, S-hydroxy-n-alkyl-lsulfonates and mixtures thereof, in which the n-alkyl radical contains from about 10 to about 24 carbon atoms.

It has been surprisingly discovered according to the present invention that the water soluble 3-, 4-, and 5- hydroxy-n-alkyl-l-sulfonates offer unique advantages not heretofore thought possible when used in combination with the builder compounds disclose-d hereinafter.

Specific examples of hydroxy alkyl sulfonates which oifer these unique advantages are listed below. Sodium is used only as a representative water soluble salt form in the following list of compounds:

sodium 3-hydroxy-n-decyl-lxsulfonate, sodium 3-hydroxy-n-dodecyl-l-sulfonate, sodium 3-hydroxy-n-tetradecyl-l-sulfonate, sodium .3-hydroxy-n-hexadecyl-l-sulfonate, sodium 3-hydroxy-n-octadecyl-l-sulfonate, sodium 3-hydroxy-n-eicosyl-l-sulfonate, sodium 3-hydroxy-n-docosyl-1-sulfonate, sodium 3-hydroxy-n-tetracosyl-l-sulfonate, sodium 4-hydroxy-n-decyl-l-sulfonate, sodium 4-hydroxy-n-dodecyl-l-sulfonate, sodium 4-hydroxy-n-tetradecyl-l-sulfonate, sodium 4-hydroxy-n-hexadecyl-l sulfonate, sodium 4-hydroxy-n-octadecyl-l-sulfonate, sodium 4-hydroxy-n-eicosyl-l-s-ulfonate, sodium 4-hydroxy-n-docosyl-l-sulfonate, sodium 4-hydroxy-n-tetracosyl-l-sulfonate, sodium S-hydroxy-n-decyl-l-sulfouate, sodium 5-hydroxy-n-dodecyl-l-sulfonate, sodium S-hydroxy-n-tetradecyl-l-sulfonate, sodium S-hydroxy-n-hexadecyl-l-sulfonate, sodium 5-hydroxy-n-octadecyl-l-sulfonate, sodium S-hydroxy-n-eicosyl-l-sulfonate, sodium S-hydroxy-n-docosyl-l-sulfonate, and sodium S-hydroxy-n-tetracosyl-l-sulfonate Mixtures of these compounds can also be used as the active detergent component in a built detergent composition according to the present invention. The 4-hydroxy species represent a preferred embodiment. Thus, a preferred built detergent composition of the present invention is one in which the active detergent ingredient is a 4-hydroxy-n-alkyl-l-sulfonate or one in which a 4-hydroxy compound is used in admixture with 3-hydroxy and S-hydroxy compounds. In mixtures with these compounds, the 4-hydroxy compound, according to this invention, is to be present as a major portion of the mixture. The term major portion means that in a binary mixture of a 4-hydroxy with either a 3-hydroxy or a 5- hydroxy compound, the 4-hydroxy compound is present in excess of 50% by weight of the active detergent ingredient. In a ternary mixture consisting of a 3-hydroxy,

4-hydroxy and a 5-hydroxy compound, the term major portion means that the 4-hydroxy is present at a percentage level greater than each of the other two compounds but not necessarily greater than the other two combined. 1

The hydrocarbon alkyl group of the hydroxy sulfonates, as indicated previously, can contain from about 10 carbon atoms up to about 24 carbon atoms. A preferred range is from 12 carbons to 18 carbons, with more preferred compounds containing 16 to 18 carbon atoms. Thus, considering the position of the hydroxyl group and the length of the aliphatic radical, the preferred hydroxy sulfonate detergent compounds for use in built detergent compositions according to the present invention are sodium and potassium 4-hydroxy-n-hexdecyll-sulfonate, 4-hydroxy-n-octadecyl-l-sulfonate or mixtures thereof.

The following examples are illustrative of the actives or mixtures of actives which can be used to formulate the preferred built detergent compositions of the invention. It is noted that these active detergents are used in admixture with other ingredients such as builders in formulating complete detergent compositions.

EXAMPLE III Sodium 4 hydroxy-n-hexadecyl-l-sulfonate, as of active detergent.

The detergent compositions of the present invention are usually used in admixture with other materials to form complete formulations. Such complete formulations are prepared commercially in several forms including granular, flake, liquid and tablet forms. More especially, when the compositions of the present invention are to be used in built formulations, they will be combined with builder compounds. Such built detergent compositions can contain as detergent actives the compositions described above, and as builders, Water soluble inorganic alkaline builder salts, water soluble organic alkaline builder salts, or mix- .tures thereof. When the compositions of the present invention are used in combination with such builder materials, they should be employed in a ratio of active detergent to builder of from about 10: to about 1:10. A preferred ratio of such mixtures is from about 2:1 to about 1:5. Examples of builders which can be used successfully in admixture with detergent compositions of the present invention are listed below.

Water soluble inorganic alkaline builder salts used alone or in admixture are alkali metal carbonates, borates, phosphates, condensed polyphosphates, bicarbonates and silicates. (Ammonium or substituted ammonium salts can also be used.) Specific examples of such salts'are sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, sodium bicarbonate, potassium tripolyphosphate, sodium hexametaphosphate, sodium sesquicarbonate, sodium monoand diortho phosphate and potassium bicarbonate.

Examples of organic alkaline builder salts Which can be used alone or in admixture are alkali metal, ammonium or substituted ammonium, aminopolycarboxylates, e.g., sodium and potassium N (2 hydroxyethyl) ethylenediaminetriacetates, sodium and potassium nitrilotriacetates and sodium, potassium and triethanolammonium N (2 hydroxyethyl)-nitrilodiacetates. Mixed salts of these polycarboxylates are also suitable. Other valuable polycarboxylic builder compounds are the sodium and potassium salts of polymaleate, polyitaconate, and polyacrylate. The alkali metal salts of phytic acid, e.g., sodium phytate, are also suitable as organic alkaline builder salts (see US. Patent 2,739,942.).

Polyphosphonates are also valuable builders in terms of the present invention including specifically sodium and potassium salts of ethane-l-hydroxy-1,1-diphosphonate, sodium and potassium salts of methylene diphosphonate, sodium and potassium salts of ethylene diphosphonate, and sodium and potassium salts of ethane 1,1,2 triphosphonate. Other examples include the alkali metal salts of ethane 2 carboxy 1,1 diphosphonic acid, hydroxymethanediphosphonic acid, carbonyldiphosphonic acid, ethane 1 hydroxy 1,1,2 triphosphonic acid, ethane- 2 hydroxy 1,1,2 triphosphonic acid, propane 1,1,3,3- tetraphosphonic acid, propane 1,1,2,3 tetraphosphonic acid, and propane l,2,2,3-tetraphosphonic acid.

The built detergent compositions prepared according to the present invention are preferably used at a pH in aqueous solution within a range of from about 9 to about 12, and preferably between 10 and 11.5.

The detergent actives of the present invention find special application in formulating built liquid detergents. Their excellent solubility characteristics make them especially useful for this type of product. The more preferred builders for use in such built liquid compositions are the potassium salts of the above listed builders and more especially potassium pyrophosphate and the potassium salt of ethane-l-hydroxy-1,1-diphosphonate.

In addition to being mixed with builder materials, the detergent compositions of the present invention can be used together with other well known detergent active compounds including, for example, anionic, nonionic, ampholytic and zwitterionic synthetic detergents and mixtures thereof. Anionic detergents can be used which are both soaps and non-soaps. For example, the sodium, potassium, and alkylol ammonium salts of higher fatty acids (C -C can be used in admixture with the detergent compositions of this invention. It will also be understood that the compositions of the present invention may contain adjuvants, diluents and additives inclusives of germicidal agents, anti-tarnishing agents, anti-redeposition agents, bactericidal agents, dyes, fluorescers and the like, without detracting from the advantageous properties of the composition.

The remarkable properties of the novel compositions of the present invention were discovered by conducting several evaluations which measure diiferent areas of detergency performance. The compositions of the present invention were then compared in performance with the performance results obtained with two other very well known detergent materials. One benchmark was sodium dodecyl benzene sulfonate (ABS) wherein the dodecyl radical is derived from tetrapropylene. The other benchmark was tallow alkyl sulfate (TAS) wherein the alkyl portion ranges from 16 to 18 carbon atoms. Dodecyl benzene sulfonate, referred to hereinafter as ABS, is a detergent material which has found wide product application. Likewise, sodium tallow alkyl sulfate, referred to hereinafter as TAS, is also a well known detergent surfactant. It is derived by sulfation of tallow fatty alcohols.

Tests described below were run with a built detergent composition made up in situ in the wash water according to the following formulation by adding the appropriate chemicals prior to addition of the articles to be washed. The percentages, unless otherwise specified, are by weight.

Percent Active detergent 20 Sodium tripolyphosphate 50 Sodium silicate (ratio of Na O:SiO of 2.4:1) 6 Sodium sulfate 24 Evaluations were made by preparing several compositions in which representative detergents prepared according to this invention, and ABS and TAS were used, on an equal weight basis, as the active detergent ingredient in the above formula.

The following active detergent compositions were selected as being representative of the present invention and were used as the Active Detergent ingredient in the standard formula listed above.

EXAMPLE VIII A detergent active composition referred to herein as C -Based Active Detergent and having the following composition, percentages being by weight:

Component A Percent C H CH=CHSO Na C H CH=CHCH SO N8 3 3 C H CH=CHCH CH SO Na C H CH CHCH CH CH SO NEL 6 Total 65 Component B C H CH(OH)CH CH SO Na 20 C H CH(OH)CH CH CH SO Na 5 Total 25 Component C Percent C H CH:CHCH(SO Na)CH (SO Na) 4.5 C H CH=CHCH=(SO Na)CH CH (SO Na) 1.5 C H CH(OH)CH CH(SO Na)CH (SO Na) 3 C H OH'(OH)CH CH(SO Na)CH CH (SO Na) 1 Total 1(l EXAMPLE IX A detergent composition referred to herein as C Based Active Detergent and having the following composition, percentages being by weight:

Component A Total EXAMPLE X A detergent composition referred to herein as O -Based Active Detergent and having the following composition, percentages being by weight:

EXAMPLE XI A detergent composition referred to herein as a C C -Based Active Detergent and having the following composition, percentages being by weight. This composition is a mixture of equal quantities of the compositions described above in Example IX and Example X.

Component A Percent C H CH=CHSO Na 6.5 C H CH=CHCH SO Na 16.5 C; 2I I25(:II CIICIIgCtI'IzSO3 N :1 6.5 3 .0 C H CH=CHSO Na 6.5 C H CH=CHCH SO Na 16.5 C H CH=CHCH CH SO Na 6.5 C H CH=OHCH CH CH SO Na 3 .0

Total 65 Component B Percent C H CH OH) CH CH SO Na 10.0 C H CH (OH) CH CH CH SO Na 2.5 C H CI-I(OH)CH CH SO Na 10.0 C H OH (OH) CH CH CH SO Na 2.5

Total 25 Component C Percent C H CH=CHCH(SO Na) CH SO Na 2.25 C H CH==CHCH(SO Na) CH CH SO Na .75 C H CH(OH)CH CH(SO Na)CH (SO Na) 1.5 C11H23CH CHZCHZ (SO Na) .5 C H CH=CHCH(SO Na) CH (SO Na) 2.25 C H CH=CHCH(SO Na)CH CH (SO Na) .75 C H CH(OH)CH CH(SO Na)CH (SO Na) 1.5 C13H27CH( OH) CH CH(SO Na) CH CH (SO Na) .5

Total EXAMPLE XII A detergent composition referred to herein as a C C C -Based Active Detergent and having the following composition, percentages being by weight.

1 4 Component A Percent C H CH=CHSO Na 4.3 C H CH=CHCH SO NZ1 1 1.0 4.3

C H CH=CHCH CH CH S0 N21 C I-I CH=CHSO Na 4.3 C H CH CHCH SO N21 1 1.0 C H CH=CHCH CH SO Na 4.3 C H CI-I CHCH CH CH S0 N53 2.0 C H CH CHSO NPL 4.3 C H CH=CHCH SO Na 11.0 C H CH=CHCH CH SO Na C H CH=CHCH CH CH SO Na 2.0

Total 64.8

Component B Percent C H CH(OH)CH2CH SO Na 6.6

C H CH(OI-I)CH CH CH SO Na C13H2I1CH(OH)CH2CH2SO3N3 C H CH (OH) CH CH CH SO Na 1.6 C15H31CH(OH) CH CH SO Na 6.6 C H CH (OH) CH CH CH SO Na 1.6

Total -I 24.6

Component C Percent 1.5 C H CH=CHCH (SO Na CH CH (SO Na) .5 C H CH(OH)CH CH(SO Na)CH (SO Na) 1.0 C H CH(OH) CH OH(SO Na CH CH (SO Na) .5 C H CH=CHCH(SO Na) CH (SO Na) 1.5 C H CH=CHCH(SO Na) CH CH (SO Na) .5 C H CH(OH)CH CH(SO Na)CH (SO Na) 1.0 C H CH(OH)CH CH(SO Na)CH CH (SO Na) .5 C H CH=CHCH(SO Na) CH (SO Na) 1.5 C13H27CH=CHCH SO Na )CH CH (SO Na) .5 C H CH(OH)CH CH (SO Na) CH ('SO Na) 1.0 C13H27CH( OH) CH CH ('SO Na )CH CH (SO Na) .6

Total 10.6

EXAMPLE XIII An Active Detergent comprising of sodium 4- hydroxy-n-hexadecyl-l-sulfonate.

The several compositions were tested as follows: Naturally soiled cotton garments and also unsoiled whiteness maintenance cotton terry cloths were washed with the above detergent formulation for ten minutes in an agitator-type automatic washing machine. The water solution had an initial pH of about 10, the water hardness was 7 grains per gallon and the product concentration in the washing solution was 0.1%. A series of tests was run with washing temperature of 80 F. and another series at F. After washing, the garments and whiteness maintenance cloths were visually compared with similar pieces, similarly soiled and washed with like detergent formulations differing only in the composition of the detergent active.

The visual comparison of the washed materials was made by a group of several people for each test. Each formed their own judgments independently and without knowledge of which actives were involved. Separate comparisons were made for cleaning and for whiteness maintenance, in both the cool water series of tests and the hot water series. The combined data from the visual judgments were recorded on a scale on which a value of 7.0 represented the cleaning and whiteness maintenance results obtained with the widely used ABS detergent as the active in the composition used at 130 F. wash temperatures.

If the soiled materials used in these tests were washed in water alone they would grade near zero on the scale. ABS performance in 130 F. washing solution is thus established as a benchmark. Values on the scale higher than 7 were awarded to improved detergency performance results. The primary value and purpose of this grading system is to ascertain the relative performance properties of detergent compounds being tested.

The results of these tests are presented in the following table.

It will be observed from column 1 of Table II that TAS has dropped below the cleaning performance level offered by ABS. However, all of the compositions prepared according to the present invention, resulted in performance levels well above the ABS scores.

The performance of the sodium 4-hydroxy-n-hexadecyll-sulfonate, Example XIII, is exceptionally remarkable.

TABLE I.PERFOR1\IANCE AT 130 F.

Detergency Rating (301.1 001.2 001.3 Examples Active Detergent Cleaning, Whiteness Average 130 F. Wash Maintenance, Detergency Solution 130 F. Wash Rating Solution Benchmark... Tetrapropylene Benzene Sulfonate (ABS).. 7. O 7.0 7.0 Do. Tallow Alkyl Sulfate (TAS) 8. 7 8. 3 8. 5 VIII Cit-Based Active Detergent 7. 6 7. 7 7. 7 IX- Clo-Based Active Detergent 9.0 8. 9 9. X. (Eng-Based Active Detergent a 9. 3 9. 7 9. XI..- ltl+O1s-B2S8d Active Detergent 9.0 8. 4 8. 7 XII C14+C1u+O1a-Based Active Detergent. 8. 2 8. 3 8. 3

It will be noted from columns 1 and 2 in Table I that the compoisitons prepared according to the present invention, e.g. Examples VIII through XII offer outstanding individual results in the important areas of cleaning and whiteness maintenance. The third column gives an Average Detergency Rating for ready comparison. In cleaning performance (col. 1) each of the compositions prepared according to the present invention scored substantially better than ABS and all but the C -Based Active Detergent and the C +C +C -Based Active Detergent scored even higher than TAS which, as those skilled in the art well appreciate, is a noteworthy achievement. In the area of whiteness maintenance, the results are equally impressive with the majority of the compositions of this invention being superior not only to ABS but also superior or equal to TAS. It is pointed out that the figures in these tables are significant primarily from the point of view that they reflect the relative performance results offered by the composition of the present invention and that they are not absolute measurements. Similarly, in arriving at an Average Detergency Rating, column 3, the purpose is to evaluate how the compositions of the present invention can be expected reliably to perform in household laundering situations in a typical washing solution of 130 F.

The detergent compositions of the present invention as shown by the performance results tabulated in Table II below, surprisingly have been found also to offer excellent cleaning and whiteness maintenance results when employed in a Washing solution having a temperature of only 80 F. This temperature is in the so-called cool water range.

As a matter of fact, the full significance of this score of 8.9 can best be appreciated by drawing a comparison between Table I results at 130 F. and this score. It will be seen that the sodium 4-hydroxy-n-hexadecyl-l-sulfonate at F. outperformed both ABS and TAS at F. There is no known precedence for this type of superiority in cleaning.

In the whiteness maintenance evaluation also (column 2), it will be seen that the compositions of the present invention offer excellent results by comparison to ABS and TAS. Column 3 of Table II indicates that, on the average, when the compositions of the present invention are employed in a washing solution having a temperature of 80 F., each of them will perform on a parity with ABS and TAS and some of them, notably, the G -containing compositions and sodium 4-hydroxy-n-hexadecyl-1-sulfonate can be expected to outperform these two widely known detergent materials. Both Table I and Table II indicate that mixtures of C +C -Based Active Detergents and C +C +C -Based Active Detergents can be used very successfully.

Although the carbon content of the active detergent compounds of the present invention has been illustrated as being even numbered chain lengths, chain lengths con taining odd numbers of carbon atoms also come within the scope hereof.

The following examples illustrate the built detergent compositions which can be prepared according to the present invention.

TABLE II.PERFORMANCE RESULTS AT 80 F.

Detergency Rating Col. 1 001.2 Col. 3 Examples Active Detergent Cleanin Whiteness, Average 80 F. Wash Maintenance, Detergency Solution 80 F. Rating Benchmark Tetrapropylene Benzene Sulfonate (ABS) 6. 4 6. 6 6. 5 D0 Tallow Alkyl Sulfate (TAS) 5. 7 7. 0 6. 3 Oil-Based Active Detergent. 6. 1 6. 9 6. 5 Chg-Based Active Detergent 7. 6 8. 4 8.0 O1SBased Active Detergent 7. 7 6. l 6. 9 C1 +O1t-Based Active Detergent 7. 3 8. 9 8. 1 Cr4+C1a+Cm-Based Active Detergent 7. 3 8. 9 8. 1 Sodium 4-hydroxy-n-hexadecyl-1-su1fonate 8. 9 8. 3 8. 6

17 18 EXAMPLE XIV EXAMPLE XVI Dlshwashmg compomwn Percent Heavy duty liquid composition Potassium-C -Based Active Detergent (as previously Percent d fi d) 10 5 C -Based Active Detergent (as previously defined) 10 P t i pyrophosphate 10 Trlpotasslum ethane-l-hydroxy-l,l-diphosphonate 20 Potassium toluene sulfonate 8 Potassium toluene ulfonate 8 Water 72 Sodium silicate 5 Potassium 4-hydroxy-n-hexadecyl-1-sulfonate and mix- 10 Water 57 ture of it with th@ Potassium Y P yand Y Q Y This built liquid composition performs well as a launn-hexadecyl-ljslllfohates can be used 111 Place of PQtaSSlum dering composition for washing heavily soiled clothes in C -Based Active Detergent in the above formulation. a laundering solution having pH f about EXAMPLE v In the following table, there are depicted built detergent 5 compositions which can be prepared according to the pres- Grmulwr laundermg composltw" ent invention. The compositions are given according to Percent i the essential ingredients of an active ingredient and a clfi'Based Acme Detergent (as Prevlously defined) builder ingredient. It is to be understood that a complete- Sodium tnpolyphosphate 50 commercial formulation can contain in addition to these Sodium i i 23 20 ingredients an addition such as inorganic alkaline salts, Sodlum slhcate 6 for example, silicates, carbonates, and sulfates, perfume, Water ""7 coloring agents, bleaching compounds, carboxymethylcel- Any of the builders listed in the description of the inllllOSfi, h y other ingredients which are Widely and vention, especially sodium ethane-1-hydroxy-l,1-diphosg r y used t0 improve the Overall Performance phonate and sodium polymaleate a be d i 1a f 25 aesthetic characteristics of detergent compositions. Each sodium tri-polyphosphate with excellent results. The pH of the Compositions Should be e in a Washing solution of the laundering solution should be about 11 for superior having a P Within a range of from about 9 about 12 results. for optimum results.

TABLE III ACTIVE DETERGENT INGREDIENT 51:25 m I X Example 11'. Eda E 111* Example IV 55151;); v*

Example VI Example VII* El 331 vr11* Example IX Example X Example XI. Eizt pie XII".

Example XIIP BUILDER INGREDIENT (a) Water soluble Inorganic:

Sodium tripolyphosphate.

Potassium tripolyphosphate- Sodium pyrophosphate.

Potassium pyrop Sodium carbonate.

Sodium hexametaphosphate.

Sodium monophosphate.

Potassium di-orthophosphate Potassium (13) Water soluble Organic:

Sodium ethylenediaminetetra- Potassium ethylenediamine- Sodium Potassium Sodium TABLE III-Continued ACTIVE DETERGENT INGREDIENT 'Irieth anolamm onium-N-(Z-hydroxyethyl)-nitrilodiaeetate Sodium polymaleate Potassium polymaleate Sodium polyltaconate Sodium polyacrylate Sodium ethane-l-hydroxy-l,l-diphosphonate Potassium ethane-l-hydroxy-l,l-

diphosphonate Sodium methylene diphosphonate.

Sodium ethane-1,1,2-triphosphonate Potassium ethane-1,1,2-triphosphonate Ratio of Active Detergent Ingredient to Builder Ingredient, Parts by Weight Examples refer to those defined and characterized in the description of the invention.

The foregoing description of the invention has been presented describing certain operable and preferred embodiments. It is not intended that the invention should be so limited since variations and modifications thereof will be obvious to those skilled in the art all of which are intended to be within the spirit and scope of the present inven tion.

It has also been discovered that the overall detergent properties of the compositions described herein can be substantially improved, and especially the sudsing properties thereof, by adding from about 0.1% to 0.3% by weight of various Water hardness salts to the detergent compositions discussed herein. A preferred level is from 0.15% to 0.25% by weight of the hardness salts, based on the weight of the total composition. Water hardness salts which can be used are magnesium and calcium salts such as magnesium chloride, magnesium sulphate, calcium chloride and calcium sulphate. Others can also be used, but the preceding ones are preferred.

It has also been discovered that the compositions of the present invention having from 20 to 24 carbon atoms possess a valuable softening property in addition to their excellent detergency properties. This provides a detergent composition having the unique and much-desired combination of cleaning and softening properties. Fabrics treated with compositions described herein having from 20 to about 24 carbon atoms are not only cleaned but also softened by the same treatment.

In accordance with this discovery, a valuable and unexpected advantage of this invention is a built detergent and softening composition comprising an active detergent and a builder, wherein the active detergent is a detergent composition which comprises from about 30% to about 70% of Component A, from about 20% to about 70% of Component B, and from about 2% to about of Component C, wherein (a) Said Component A is a mixture of double-bond positional isomers of water soluble salts of alkene-lsulfonic acids containing from about to about 24 carbon atoms, said mixture of positional isomers including about 10% to about 25% of an alpha-beta unsaturated isomer, about to about 70% of a beta-gamma unsaturated isomer, about 5% to about 25% of a gammadelta unsaturated isomer, and about 5% to about 10% of a delta-epsilon unsaturated isomer;

(b) Said Component B is a mixture of water soluble salts of bifunctionally-substituted sulfur-containing saturated aliphatic compounds containing from about 20 to about 24 carbon atoms, the functional units being hydroxy and sulfonate radicals with the sulfonate radical always being on the terminal carbon and the hydroxyl radical being attached to a carbon atom at least two carbon atoms removed from the terminal carbon atoms; and

(c) Said Component C is a mixture comprising from about 30-95% water soluble salts of alkene disulfonates containing from about 20 to about 24 carbon atoms, and from about 5% to about water soluble salts of hydroxy disulfonates containing from about 20 to about 24 carbon atoms, said alkene disulfonates containing a sulfonate group attached to a terminal carbon atom and a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, the alkene double bond being distributed between the terminal carbon atom and about the seventh carbon atom, said hydroxy disulfonates being saturated aliphatic compounds having a sulfonate radical attached to a terminal carbon, a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, and a hydroxy group attached to a carbon atom which is not more than about four carbon atoms removed from the site of attachment of said second sulfonate group; and wherein the builder is selected from the group consisting of water soluble inorganic alkaline builder salts, water soluble organic alkaline builder salts, and mixtures thereof, the weight ratio of the said detergent to said builder is in the range of from about 10:1 to about 1:10. The preferred Weight ratio of the active detergent to builder is in the range of from about 2:1 to about 5: 1.

Fabric softeners have been widley accepted as valuable detergent and laundering aids. However, a desirable softening of the laundered fabrics now. requires a separate operation or step in the laundering process. It is necessary to have a separate step due to the fact that the majority of commercially available softening compositions are cationic-based compositions. Such materials would be virtually inactivated if used in conjunction or in the presence of typical detergent compositions containing, for example, anionic detergents, due to incompatibility of cationic and anionic compounds. This means that a woman in a typical household laundering situation must be present or available to add a softening composition to the rinse water in a normal laundering cycle. At times, this may not be convenient.

With the present invention, however, this problem is solved because 'bothfunctions, i.e., cleaning and softening, can be accomplished by the same composition. Inasmuch as the compositions of the present invention are anionic, they can be used alone or in admixture with other typical anionic detergents, including the lower sulfonates of this'invention', without danger of destroying the softening properties of the compositions. The advantages of the present invention have been demonstrated by graded comparisons between fabrics laundered with built detergent and softening compositions of the present invention and conventional, commercially-available built detergent compositions. Consistently, the fabrics laundered by the compositions of the present invention are chosen by experienced, unbiased graders as being softened to a substantially greater degree than fabrics laundered in other non-softening compositions. The degree of softness obtained with the compositions of the present invention are comparable to fabrics laundered with typical detergents followed by a separate softening treatment with a specially-formulated softening composition.

The following example illustrates a detergent composition of the present invention which has both cleaning and softening properties.

EXAMPLE XVII Component A Percent C13H37CHZCHSO3NB. C H CH=CHCH SO Na 3 3 C H CH=CHCH CH SO Na 13 C15H3 6 Total 65 Component B Percent C17H CH(OH)CH CH2SO Na 2O C16H33CH(OH) CH CH CH SO Na 5 Total 25 Component C Percent C H CH C(SO Na)CH SO Na C H CH=CHCH(SO Na) CH SO Na 3.0 C H -CH=CHCH CH(SO Na) CH SO Na .5 C15H31CH2CH:CH(SO3NE1) CH CH SO Na .5 C15H31CH CHCH(SO3Na) CH CH SO Na .5 C H CH==CHCH CH (SO NQ) CH CH SO Na .5 C H CH(OH) CH CH(SO Na)CH SO Na 1.5 C H CH(OH) CH CH CI-I(SO Na) CH SO Na 1.5 C H CH(OH)CH CH(SO N8.) CH CH SO Na .5 CH CH SO Na -5 Total EXAMPLE XVIII This is an example of a formulation of a detergent composition having the unique properties of excellent cleaning coupled with desirable softening of the fabrics laundered thereby.

Percent C -based active detergent of Example XVII 17.5 Trisodium ethane-l-hydroxy-1,1-diphosphonate 50 Sodium sulfate 23 Sodium silicate 6 Water 3.5

The diphosphonate builder can be replaced in this example with sodium tripolyphosphate or trisodium nitrilotriacetate with equally good results.

What is claimed is:

1. A detergent composition consisting essentially of from about 30% to about 70% of Component A, from about 20% to about 70% of Component B, and from about 2% to about of Component C, wherein (a) said Component A is a mixture of double-bond positional isomers of water soluble salts of alkene-lsulfonic acids containing from about 10 to about 24 carbon atoms, said mixture of positional isomers including about 10% to about 25% of an alpha-beta unsaturated isomer, about 30% to about 70% of a 22 beta-gamma unsaturated isomer, about 5% to about 25 of a gamma-delta unsaturated isomer, and about 5% to about 10% of a delta-epsilon unsaturated isomer;

(b) said Component B is a mixture of water soluble salts of bifunctionally-substituted sulfur-containing saturated aliphatic compounds containing from about 10 to about 24 carbon atoms, the functional units being hydroxy and sulfonate radicals with the sulfonate radical always being on the terminal carbon and the hydroxyl radical being attached to a carbon atom at least two carbon atoms removed from the terminal carbon atom, at least of the hydroxy radical substitutions being in the 3, 4, and 5 positions; and

(c) said Component C is a mixture comprising from about 30-95% water soluble salts of alkene disulfonates containing from about 10 to about 24 carbon atoms, and from about 5% to about 70% water soluble salts of hydroxy disulfonates containing from about 10 to about 24 carbon atoms, said alkene disulfonates containing a sulfonate group attached to a terminal carbon atom and a second sulfonate group attached to an internal carbon atom not more that about six carbon atoms removed from said terminal carbon atom, the alkene double bond being distributed between the terminal carbon atom and about the seventh carbon atom, said hydroxy disulfonates being saturated aliphatic compounds having a sulfonate radical attached to a terminal carbon, a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, and a hydroxy group attached to a carbon atom which is not more than about four carbon atoms removed from the site of attachment of said second sulfonate group.

2. A detergent composition of claim 1 which comprises about 35% to about 65% of Component A, from about 25% to about 60% of Component B and from about 3% to about 12% of Component C.

-3. A built detergent composition consisting essentially of (a) an Active Detergent and ('b) a builder, wherein (a) the Active Detergent is the detergent composition of claim 1 and wherein (b) the builder is selected from the group consisting of water soluble inorganic alkaline builder salts, water soluble organic alkaline builder salts, and mixtures thereof, the weight ratio of the said Active Detergent to said builder is in the range of from about 10:1 to about 1:10.

4. A built detergent composition according to claim 3 wherein the weight ratio of said Active Detergent to said builder is in the range of from about 2:1 to about 1:5.

5. A built detergent composition according to claim 3 wherein the Active Detergent is the detergent composition of claim 2.

6. A built cool Water detergent composition consisting essentially of (a) an Active Detergent and (b) a builder wherein the Active Detergent is selected from the group consisting of water soluble S-hydroxy-n-alkyl-l-sulfonate, 4-hydroxy-n-alkyl-l-sulfonate, 5-hydroxy-n-alkyl 1 sulfonate and mixtures thereof, wherein the n-alkyl radical contains from about 10 to about 24 carbon atoms, and wherein the builder (b) is selected from the group consisting of water soluble inorganic alkaline builder salts, water soluble organic alkaline builder salts, and mixtures thereof, the weight ratio of the said Active Detergent to said builder is in the range of from about 10:1 to about 1:10.

7. A built detergent composition of claim 6 wherein the n-alkyl radical contains from about 12 to about 18 carbon atoms.

8. A built detergent composition of claim 6 wherein the Active Detergent contains 16 carbon atoms.

9. A built detergent composition of claim 6 wherein the Active Detergent composition is water soluble 4-hydroxy-n-hexadecyl-l-sulfonate.

10. A built detergent and softening composition which effectively removes soil and softens fabrics consisting essentially of from about 30% to about 70% of Component A, from about 20% to about 70% of Component B, and from about 2% to about 15% of Component C, wherein (a) said Component A is a mixture of double-bond positional isomers of water soluble salts of alkene-1- sulfonic acids containing from about 20 to about 24 carbon atoms, said mixture of positional isomers including about 10% to about 25% of an alpha-beta unsaturated isomer, about 30% to about 70% of a beta-gamma unsaturated isomer, about to about 25 of gamma-delta unsaturated isomer, and about 5% to about of a delta-epsilon unsaturated isomer;

(b) said Component B is a mixture of Water soluble salts of bifunctionally-substituted sulfur-containing saturated aliphatic compounds containing from about 20 to about 24 carbon atoms, the functional units being hydroxy and sulfonate radicals with the sulfonate radical always being on the terminal carbon and the hydr-oxyl radical being attached to a carbon atom at least two carbon atoms removed from the terminal carbon atoms at least 90% of the hydroxy radical substitutions being in the 3, 4, and 5 positions; and

(c) said Component C is a mixture comprising from about 30-95% water soluble salts of alkene disulfonates containing from about 20 to about 24 carbon atoms, and from about 5% to about 70% water soluble salts of hydroxy disulfonates containing from about 20 to about 24 carbon atoms, said alkene disulfonates containing a sulfonate group attached to a terminal carbon atom and a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, the alkene double bond being distributed between the terminal carbon atom and about the seventh carbon atom, said hydroxy disulfonates being saturated aliphatic compounds having a sulfonate radical attached to a terminal carbon, a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, and a hydroxy group attached to a carbon atom which is not more than about four carbon atoms removed from the site of attachment of said second sulfonate group; and wherein the builder is selected from the group consisting of water soluble inorganic alkaline builder 24 salts, water soluble organic alkaline builder salts, and mixtures thereof, the weight ratio of the said active detergent to said builder is in the range of from about 10:1 to about 1:10.

11. A built detergent and softening composition according to claim 10 which comprises about 35% to about 65% of Component A, from about 25% to about of Component B, and from about 3% to about 12% of Component C.

12. A built detergent and softening composition according to claim 10 wherein the weight ratio of said active detergent to said builder is in the range of from about 2:1 to about 1:5.

References Cited UNITED STATES PATENTS 2,061,517 11/1936 Downing et a1. 260513 2,061,618 11/1936 Downing et al. 260513 2,061,620 11/1936 Downing et a1. 260513 2,477,383 7/ 1949 Lewis 252-161 3,072,618 '1/1963 Turbak.

FOREIGN PATENTS 651,783 8/1964 Belgium.

OTHER REFERENCES Alpha-Olefins in the Surfactant Industry, J. Amer. Oil Chem. Society (November 1963), T. H. Liddicoot, 631- 636.

Alkene Sulfonates Made by New Method, Chemical and Engineering News, Apr. 15, 1963, A. F. Turbak, pp. 96-98.

The Reactions of Sulfur Trioxide and of Its Adducts With Organic Compounds, Chemical Review, 62, #6, pp. 549-589, December 1962.

Chem. Ber. 97, #10, 2903-13 (October 1964), Higher Molecular Aliphatic Sulfonic Acids I. Z-Hydroxy-l-n- Alkanesulfonic Acids I. Z-Hydroxy-l-n-Alkanesulfonic Acids, F. Puschel and Claus Kaiser.

Chem. Ber. 97, #10, 2917-25 (October 1964), Higher Molecular Aliphatic Sulfonic Acids II, 3-Hydroxy-l-n- Alkanesulfonic Acids and Their Inner Esters (1,3-Sultones), F. Puschel and Claus Kaiser.

Chem. Ber. 97, #10, 2926-33 (October 1964), Higher Molecular Unsaturated Sulfonic Acids and the Hydrolysis of 1,3-Alkanesultones, F. Puschel and Claus Kaiser.

Chem. Ber. 98, 735-742 (1965), Higher Molecular Aliphatic Sulfonic Acids. IV, Sulfonation of Unbranched Alpha-Olefins With SO F. Puschel and Claus Kaiser.

LEON D. ROSDOL, Primary Examiner. S. E. DARDEN, Examiner. 

1. A DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF FROM ABOUT 30% TO ABOUT 70% OF COMPONENT A, FROM ABOUT 20% TO ABOUT 70% OF COMPONENT B, AND FROM ABOUT 2% TO ABOUT 15% OF COMPONENT C, WHEREIN (A) SAID COMPONENT A IS A MIXTURE OF DOUBLE-BOND POSITIONAL ISOMERS OF WATER SOLUBLE SALTS OF ALKENE-1SULFONIC ACIDS CONTAINING FROM ABOUT 10 TO ABOUT 24 CARBON ATOMS, SAID MIXTURE OF POSITIONAL ISOMERS INCLUDING ABOUT 10% TO ABOUT 25% OF AN ALPHA-BETA UNSATURATED ISOMER, ABOUT 30% TO ABOUT 70% OF A BETA-GAMMA UNSATURATED ISOMER, ABOUT 5% TO ABOUT 25% OF A GAMMA-DELTA UNSATURATED ISOMER, AND ABOUT 5% TO ABOUT 10% OF A DELTAEPSILON UNSATURATED ISOMER; (B) SAID COMPONENT B IS A MIXTURE OF WATER SOLUBLE SALTS OF BIFUNCTIONALLY-SUBSTITUTED SULFUR-CONTAINING SATURATED ALIPHATIC COMPOUNDS CONTAINING FROM ABOUT 10 TO ABOUT 24 CARBON ATOMS, THE FUNCTIONAL UNITS BEING HYDROXY AND SULFONATE RADICALS WITH THE SULFONATE RADICAL ALWAYS BEING ON THE TERMINAL CARBON AND THE HYDROXYL RADICAL BEING ATTACHED TO A CARBON ATOM AT LEAST TWO CARBON ATOMS REMOVED FROM THE TERMINAL CARBON ATOM, AT LEAST 90% OF THE HYDROXY RADICAL SUBSTITUTIONS BEING IN THE 3,4, AND 5 POSITIONS; AND (C) SAID COMPONENT C IS A MIXTURE COMPRISING FROM ABOUT 30-95% WATER SOLUBLE SALTS OF ALKENE DISULFONATES CONTAINING FROM ABOUT 10 TO ABOUT 24 CARBON ATOMS, AND FROM ABOUT 5% TO ABOUT 70% WATER SOLUBLE SALTS OF HYDROXY DISULFONATES CONTAINING FROM ABOUT 10 TO ABOUT 24 CARBON ATOMS, SAID ALKENE DISULFONATES CONTAINING A SULFONATE GROUP ATTACHED TO A TERMINAL CARBON ATOM AND A SECOND SULFONATE GROUP ATTACHED TO AN INTERNAL CARBON ATOM NOT MORE THAT ABOUT SIX CARBON ATOMS REMOVED FROM SAID TERMINAL CARBON ATOM, THE ALKENE DOUBLE BOND BEING DISTRIBUTED BETWEEN THE TERMINAL CARBON ATOM AND ABOUT THE SEVENTH CARBONATOM, SAID HYDROXY DISULFONATES BEING SATURATED ALIPHATIC COMPOUNDS HAVING A SULFONATE RADICAL ATTACHED TO A TERMINAL CARBON, A SECOND SULFONATE GROUP ATTACHED TO AN INTERNAL CARBON ATOM NOT MORE THAN ABOUT SIX CARBON ATOMS REMOVED FROM SAID TERMINAL CARBON ATOM, AND A HYDROXY GROUP ATTACHED TO A CARBON ATOM WHICH IS NOT MORE THAN ABOUT FOUR CARBON ATOMS REMOVED FROM THE SITE OF ATACHEMENT OF SAID SECOND SULFONATE GROUP. 